CN100349929C - Clear and flexible propylene polymer compositions - Google Patents
Clear and flexible propylene polymer compositions Download PDFInfo
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- CN100349929C CN100349929C CNB028235967A CN02823596A CN100349929C CN 100349929 C CN100349929 C CN 100349929C CN B028235967 A CNB028235967 A CN B028235967A CN 02823596 A CN02823596 A CN 02823596A CN 100349929 C CN100349929 C CN 100349929C
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D7/00—Containers having bodies formed by interconnecting or uniting two or more rigid, or substantially rigid, components made wholly or mainly of metal
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/10—Chemical modification of a polymer including a reactive processing step which leads, inter alia, to morphological and/or rheological modifications, e.g. visbreaking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
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Abstract
A propylene polymer composition having a melt flow rate (MFR) value from 3 to 30 g/10 min, comprising (percent by weight): A) 50-90% of one or more propylene copolymer(s) having a content of xylene-insoluble mojety at room temperature of not less than 85%, selected from the group consisting of propylene-ethylene random copolymers containing from 1 to 7%, of ethylene; propylene-C4-C8 alpha-olefin copolymers containing 2-10% of the C4-C8 alpha-olefins; and propylene-ethylene-C4-C8 a-olefin copolymers containing 0.5-5% of ethylene and 2-6% Of C4-C8 alpha-olefins; and B) 10-50% of a copolymer of propylene containing from 8 to 40% of ethylene and optionally 1-10% of a C4-C8 alpha-olefin; the said MFR value (MFR (2)) being obtained by subjecting to degradation a precursor composition comprising the same components A) and B) in the above said proportions, but having the MFR value (MER (1)) from 0.1 to 5 g/10 min with a ratio MFR (2) to MFR (1) of from 1.5 to 20.
Description
The present invention relates to the thermoplastic elastic prolylene polymer composition and by the goods of its production.
The composition of Miao Shuing is particularly suited for making film and injection-molded item hereinafter.Especially, described goods have good kindliness, good impact property (even at low temperatures), good optical character, the especially transparency and low chemical substance burst size.Therefore, described goods especially are suitable for and Food Contact.
Well-known in the prior art is that for producing the softish multipolymer, high dimethylbenzene-soluble fractions is desirable.Yet high dimethylbenzene-soluble fractions value causes a large amount of hexane extractable matters, so that this softish multipolymer is not suitable for the food product pack field.The advantage of the present composition is that they have the amount of low hexane extractable matter, have the amount of higher xylene soluble part simultaneously.
Therefore composition of the present invention has especially valuable balance at dimethylbenzene-soluble fractions and hexane-can extract between the part.Said composition has low modulus in flexure value and low hexane extractable under desirable flowability.
Therefore, the invention provides prolylene polymer composition, its melt flow rate (MFR) (MFR) value is 3 to 30g/10min, preferred 3 to 20g/10min, most preferably 3 to 15g/10min, and it comprises (weight percentage):
A) one or more propylene copolymers of 50 to 90%, preferred 60 to 85%, this propylene copolymer under room temperature (about 23 ℃) in dimethylbenzene the content of insoluble part be not less than 85%, preferably be not less than 90%, this propylene copolymer is selected from that (A1) comprises 1 to 7%, the propylene of preferred 1.5 to 6% ethene and the random copolymers of ethene; (A2) comprise the C of 2-10%
4-C
8The propylene of alpha-olefin and one or more C
4-C
8The multipolymer of alpha-olefin; (A3) comprise the ethene of 0.5-5% and the C of 2-6%
4-C
8The propylene of alpha-olefin and ethene and one or more C
4-C
8The multipolymer of alpha-olefin; With
B) 10 to 50%, preferred 15 to 40% comprise 8 to 40%, preferred 8 to 30%, most preferably 10 to 28% ethene and the C of 1-10% randomly
4-C
8The multipolymer of the propylene of alpha-olefin;
Described MFR value (MFR (2)) comprises identical multipolymer (A) and precursor composition (B) with ratio as mentioned above and degrades and reach by making, but the MFR value that has (MFR (1)) is 0.1 to 5g/10min, preferred 0.5 to 4g/10min, and MFR (2) is 1.5 to 20, preferred 2 to 15 with the ratio of MFR (1) simultaneously.
Can be clear that from above definition term " multipolymer " comprises the polymkeric substance that comprises more than a kind of comonomer.
Can be used as comonomer and be present in C in described propene polymer or the polymer composition
4-C
10Alpha-olefin is by general formula CH
2=CHR represents that wherein R is the alkyl with straight or branched of 2-8 carbon atom, perhaps aryl C for example
6-C
10Aryl (especially phenyl).Described C
4-C
10The example of alpha-olefin is 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and 1-octene.Especially preferred is 1-butylene.
As mentioned above, the MFR value that the precursor polymeric compositions of producing in polymerization process has is 0.1 to 5g/10min, preferred 0.5 to 4g/10min, according to ISO method 1133 (230 ℃ 2.16kg) are measured.Then,, described composition is carried out the chemical degradation of polymer chain and handle (viscosity breaking), so that the MFR value that obtains to require according to described method mensuration according to method well-known in the art.The chemical degradation of polymkeric substance for example carries out in the presence of the superoxide at radical initiator.The example that can be used for the radical initiator of this purpose is 2,5-dimethyl-2,5-two (tert-butyl peroxide)-hexane and dicumyl peroxide.
Degradation treatment uses the radical initiator of appropriate amount to carry out, and preferably for example carries out in the nitrogen at inert atmosphere.Method as known in the art, device and operational condition all can be used for the enforcement of this method.
Most preferred prolylene polymer composition of the present invention comprise surpass 60 to 85% weight multipolymer (A) and 15 to the multipolymer that is lower than 40% weight (B).
The modulus in flexure that described prolylene polymer composition has usually be lower than 500MPa, preferably be lower than 450MPa, most preferably be lower than 400MPa.
In prolylene polymer composition of the present invention, hexane can extract part and preferably be lower than 5.5wt%, especially is lower than 4.5wt%, measures according to the method for hereinafter describing.
Dimethylbenzene-the soluble fractions of prolylene polymer composition of the present invention is preferably 18 to 45wt%, most preferably 22 to 35wt%.Ethylene content is that preferred 18 to 30wt%, more preferably 20 to 38wt%, most preferred scope is 20 to 25wt% in described part.
Usually dimethylbenzene-soluble fractions and hexane-can the extract weight ratio between the part is greater than 4.
The haze value that prolylene polymer composition of the present invention has usually is lower than 20%, preferably is lower than 18%, according to the method for hereinafter describing film or plaque is carried out.
In addition, the present invention also provides the effective and inexpensive method that is used to prepare described prolylene polymer composition.This method comprised with the next stage:
1) in the step of at least two orders by making monomer polymerization prepare foregoing precursor composition, wherein multipolymer (A) and (B) independently the order step in prepare, in each step at the polymkeric substance that forms be used for operating in the presence of the catalyzer in preceding step, and with the amount adding molecular weight regulator (preferably hydrogen) of MFR (1) value that can obtain 0.1 to 5g/10min, preferred 0.5 to 4g/10min precursor composition; With
2) with 1) in the precursor composition of preparation carry out degradation treatment so that the MFR of final composition (2) value reaches 3 to 20g/10min, preferred 3 to 15g/10min, the degraded ratio of representing with the ratio of MFR (2) and MFR (1) is 1.5 to 20, preferred 2 to 15.
This preferable methods is very easily, because it has avoided the component (being multipolymer) and the independent degradation treatment of independent preparation precursor composition.
Can be clear that from the description of front in precursor composition, the relative quantity of co-monomer content and multipolymer (A) and (B) is identical with final composition (after degraded).Degradation treatment has the MFR value that makes composition and brings up to the effect of MFR (2) from MFR (1), the ratio between two MFR values, and promptly MFR (2)/MFR (1) is 1.5 to 20, preferred 2 to 15.
Composition of the present invention can be prepared by the polymerization in two or more polymerization procedures.This class is aggregated under the existence of stereospecific Ziegler-Natta catalyst carries out.The main ingredient of described catalyzer is an ingredient of solid catalyst, and it comprises: have the titanium compound of at least one titanium-halogen key, and electronics-donor compound, both all load on the magnesium halide of activity form.Another main ingredient (promotor) is an organo-aluminium compound, for example al-alkyl compound.
Randomly add external donor.
The normally used catalyzer of the inventive method can be produced polypropylene, the insoluble value of this polypropylene dimethylbenzene at ambient temperature greater than 90%, be preferably greater than 95%.
Catalyzer with above-mentioned feature is well-known in patent documentation; Especially advantageously be described in United States Patent (USP) 4,399,054 and European patent 45977 in catalyzer.Other examples can see United States Patent (USP) 4,472,524.
The ingredient of solid catalyst that is used for described catalyzer, comprise be selected from following as electronics-the give compound of body (the inner body of giving): ether, ketone, lactone, comprise the compound of N, P and/or S atom, and single-and the ester of dicarboxylic acid.Especially electronics-the donor compound of Shi Heing is 1 of a following general formula, the 3-diether:
Wherein, R
IAnd R
IIBe same or different and be C
1-C
18Alkyl, C
3-C
18Cycloalkyl or C
7-C
18Aromatic yl group; R
IIIAnd R
IVBe same or different and be C
1-C
4Alkyl; Or such 1, the 3-diether, wherein 2 carbon atom belongs to by 5 in the position, 6 or 7 cyclic or polycyclic structures that carbon atom is formed, perhaps by 5-n or the individual carbon atom of 6-n ' and cyclic or the polycyclic structure formed of n nitrogen-atoms and the individual heteroatoms of n ' correspondingly, described heteroatoms is selected from N, O, S and Si, wherein n be 1 or 2 and n ' be 1,2 or 3, described structure comprises two or three unsaturated link(age)s (ring-type polyene structure), and randomly with other ring texture condensations, perhaps replaced by one or more substituting groups, described substituting group is selected from the straight or branched alkyl; Cycloalkyl, aryl, aralkyl, alkylaryl group and halogen perhaps replace with other ring texture condensations with by one or more above-mentioned substituting groups, and this substituting group also can be keyed to the ring texture of condensation; The ring texture of the one or more and condensation of above-mentioned alkyl, cycloalkyl, aryl, aralkyl or alkylaryl group randomly comprises one or more alternative carbon or hydrogen atom or both heteroatomss.
This class ether is described in disclosed european patent application 361493 and 728769.The representational example of described diether is 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 9, two (methoxymethyl) fluorenes of 9-.
Other electronics-donor compounds that are fit to are phthalic esters, for example diisobutyl, dioctyl, phenylbenzene and benzyl butyl phthalate.
The preparation of above-mentioned catalyst component is carried out according to diverse ways.
For example, MgCl
2-nROH affixture (the especially form of spheroidal particle), wherein n be generally 1 to 3 and ROH be ethanol, butanols or isopropylcarbinol, with the excessive TiCl that comprises electronics-donor compound
4Reaction.Temperature of reaction is generally 80 to 120 ℃.Isolate solid then, and in the presence of electronics-donor compound or do not having to make under the situation of electronics-donor compound itself and a TiCl
4Reaction is again washed with its separation and with the aliquots containig of hydrocarbon, then up to removing whole chlorions.
In ingredient of solid catalyst, titanium compound is represented with Ti, and the amount with 0.5 to 10% weight exists usually.The amount of the electronics-donor compound that keeps with the form that is fixed on the ingredient of solid catalyst is 5 to 20% moles with respect to magnesium dihalide usually.
The titanium compound that can be used to prepare ingredient of solid catalyst is the halogenide and the halogenohydrin salt of titanium.Titanium tetrachloride is preferred compound.
Above-mentioned reaction has formed the magnesium halide of activity form.Also known other reaction from document, these reactions can begin to form the magnesium halide of activity form from magnesium compound, for example magnesium carboxylates of non-halide.
Comprise trialkylaluminium as the alkylaluminium cpd of promotor, for example triethyl aluminum, triisobutyl aluminium, three n-butylaluminum and comprise two or more via O or N atom or SO
4Perhaps SO
3Group is the linearity or the cyclic alkylaluminium cpd of the aluminium atom of keyed jointing each other.
Alkylaluminium cpd uses than the amount that is 1 to 1000 with Al/Ti usually.
Can comprise for example phenylformic acid alkyl ester of aromatic esters as the electronics-donor compound of external donor, especially comprise the silicon compound of at least one Si-OR key, wherein R is a hydrocarbyl group.
The example of silicon compound is (tertiary butyl)
2Si (OCH
3)
2, (cyclohexyl) (methyl) Si (OCH
3)
2, (cyclopentyl)
2Si (OCH
3)
2(phenyl)
2Si (OCH
3)
2Can also advantageously use and have 1 of above-mentioned general formula, the 3-diether.If inner is a kind of in these diether to body, then external donor can save.
Especially, though many other combinations of catalyst component noted earlier can be used to prepare prolylene polymer composition of the present invention, random copolymers preferably uses and comprises that phthalic ester gives body and (cyclopentyl) as inside
2Si (OCH
3)
2As external donor or described 1, the 3-diether prepares for the catalyzer of body as inside.
As previously described, polymerization process can be carried out in two or more steps.Polymerization procedure preferably the order, promptly in the step of the order of separating, prepare first propylene copolymer, multipolymer (A) for example, with second multipolymer, multipolymer (B) for example, in each step, except that first step, in the presence of polymkeric substance that forms and the catalyzer that uses in the step in front, operate.Obviously, when composition comprises additional polymkeric substance, must increase other polymerization procedure to produce them.Described polymerization procedure can carry out in independent reactor, perhaps carries out in the reactor of the one or more gradients that has wherein produced monomer concentration and polymerizing condition.Catalyzer mostly just adds in the first step, yet the activity that it had makes it remain active in whole steps subsequently.
The regulation and control of molecular weight are undertaken by using known conditioning agent, especially hydrogen.
By suitably in relevant step, regulating the concentration of molecular weight regulator, can obtain previously described MFR value.
Whole polymerization processes, it can be successive or intermittence, carries out in liquid phase or in gas phase according to known technique and in the inert diluent existence or not, is perhaps undertaken by blended liquid-gas technology.
Reaction times, the pressure and temperature in two steps are not crucial, yet preferably temperature is 20 to 100 ℃.Pressure can be normal atmosphere or higher pressure.
Catalyzer can contact (prepolymerization) with a spot of alkene in advance.
According to preferred polymerization process, composition of the present invention is produced by the polymerization process of aforesaid order, and (A) is prepared by the gas phase polymerization process that carries out in the polymeric area of at least two interconnection except multipolymer.
Be used for being described in EP application 782587 according to the method for fs of preferable methods polymerization multipolymer (A).
At length, described method comprises: one or more monomers are being fed to described polymeric area and from described polymeric area collected polymer product in the presence of the catalyzer, under reaction conditions.In described method, the polymer beads that increases upwards flows through (first) of described polymeric area (lifter) under fluidization conditions fast, leave this lifter and enter another (second) polymeric area (downtake), form with densification flows downward under action of gravity by this polymeric area, leave described downtake and import described lifter again, so the circulation of between lifter and downtake, having set up polymkeric substance.
In downtake, arrived the solid high intensity values, it is near the tap density of polymkeric substance.Like this, can obtain the postiive gain of pressure along flow direction, so that polymkeric substance can be imported lifter again, and need be by means of special mechanical means.Set up " loop " circulation like this, it is limited by pressure equilibrium between two polymeric areas and the loss of pressure head that is introduced into system.
Usually, the quick fluidizing condition in lifter is by setting up comprising about monomeric gaseous mixture is fed in the described lifter.Preferably the charging of gaseous mixture is below polymkeric substance is introduced the point of described lifter again, undertaken by using (if suitably) gas distributor device.Carrier gas enters the speed of lifter greater than the transport velocity under operational condition, is preferably 2 to 15m/s.
Usually, polymkeric substance and the gaseous mixture that leaves lifter is transported to the solid/gas separation district.Solid/gas separation can use conventional separating device to carry out.Polymkeric substance enters downtake from the disengaging zone.The gaseous mixture that leaves the disengaging zone is compressed, cools off and transfer to lifter, if suitably, adds the monomer and/or the molecular weight regulator that replenish.Can shift by the circular route of gaseous mixture.
The equipment that the control of polymkeric substance round-robin between two polymeric areas can be suitable for controlling solid flow by use is machinery valve for example, and metering is left the amount of the polymkeric substance of downtake and carried out.
Operating parameters, temperature for example is common those in the gas-phase olefin polymerization process, for example between 50 to 120 ℃.
This fs technology can 0.5 and 10MPa between working pressure, preferred 1.5 to 6MPa between working pressure under carry out.
Advantageously, in polymeric area, keep one or more rare gas elementes, its amount make the sum of dividing potential drop of rare gas element be preferably total gas pressure 5 and 80% between.Rare gas element can be for example nitrogen or propane.
Different catalyzer can be fed to lifter in any point of lifter.Yet they also can be in any point of downtake charging.Catalyzer can be any physical condition, therefore can use solid-state or liquid catalyzer.
In the subordinate phase of preferred polymerization process, multipolymer (B) uses conventional fluidized-bed gaseous techniques to produce usually.
Composition can also by use identical catalyzer with basically with identical polymerizing condition explained before under (except described multipolymer will independently prepare in the polymerization procedure) operate and prepare described multipolymer respectively, mechanically the described multipolymer of blended melting state obtains then.Can use conventional mixing equipment, as screw extrusion press, twin screw extruder especially.
The propene polymer and the prolylene polymer composition that are used for goods of the present invention can also comprise the additive that is generally used for this area, for example oxidation inhibitor, photostabilizer, thermo-stabilizer, nucleator, tinting material and filler.
Especially, adding nucleator can bring important improvement aspect the important physical-mechanical property, for example modulus in flexure, heat-drawn wire (HDT), yield tensile strength and the transparency.
The representative instance of nucleator is p-tert-butyl benzoic acid ester and 1,3-and 2,4-dibenzylidene sorbitol.
Nucleator is preferably with respect to gross weight to be 0.05 to 2% weight, the more preferably amount adding of 0.1 to 1% weight.
Add mineral filler, for example talcum, lime carbonate and mineral fibre, also for example modulus in flexure and HDT bring improvement to some mechanical property.Talcum can also have nucleogenesis.
The main application fields of the present composition is cast film or sheet material and injection-molded container.Cast film or sheet material and injection-moulded parts are used to food product pack and food or beverage container especially.
Cast film of the present invention, sheet material and injection-molded item can use well-known method to be prepared.
Film of the present invention has the thickness that is generally 10 to 100 μ m, and sheet material has the thickness more than or equal to 100 μ m usually.
Cast film/sheet material of the present invention can be singly-or multiwalled film/sheet material.In multiwalled film/sheet material, the substrate layer (being also referred to as " carrier layer ") with Food Contact comprises prolylene polymer composition of the present invention at least.Other layer can comprise the polymkeric substance of other kinds, for example C
2-C
6The crystallization of alpha-olefin or semi-crystalline polymer, polymeric amide and poly-(ethene-copolymerization-vinyl acetate).Polyethylene is preferably selected from LLDPE and LDPE.This class multiwalled film/sheet material is produced by using single film/sheet material that the common process condition will be combined to carry out coextrusion.
Provide following examples further specifying the present invention, but be not used in restriction the present invention.
The data relevant with film with the polymer materials of embodiment are measured by following method of reporting.
-melt flow rate (MFR): according to ISO method 1133 (230 ℃ 2.16kg) are measured.
Solubleness in the-dimethylbenzene: according to mensuration as described below.
The polymkeric substance of 2.5 grams and 250 milliliters dimethylbenzene are added the glass flask that is equipped with refrigerator and magnetic stirrer.In 30 minutes, temperature is improved the boiling point of solvent.The clear solution that will so obtain remains on to reflux and stir and is issued to other 30 minutes then.Then airtight flask was kept 30 minutes in ice and water-bath, and in 25 ℃ hot water bath with thermostatic control, kept 30 minutes.Filtering the solid that so forms on the filter paper fast.100 milliliters filtered liquid are poured in the aluminum container of weighing in advance, it is being heated under nitrogen gas stream on hot-plate, desolvate to remove by evaporation.Then container is being kept up to reaching constant weight on 80 ℃ the baking oven, under vacuum.Calculate the weight percentage of the polymkeric substance that at room temperature dissolves in dimethylbenzene then.To at room temperature be insoluble to the weight percentage of polymkeric substance of dimethylbenzene as the isotacticity index of polymkeric substance.This value meets basically by carry out the isotacticity index of extraction and determination with the ebullient normal heptane, and it is appointed as polyacrylic isotacticity index according to definition.
-limiting viscosity (IV): in tetraline, measure down at 135 ℃.
The hexane extractable matter of-film or plaque:, measure by suspension composition sample in excessive hexane according to FDA 177,1520.Sample is film or the plaque with 100 μ m thickness.Film is by extruding preparation.Plaque prepares by compression moulding.To place 2 hours in the autoclave of suspensoid under 50 ℃.Remove hexane by evaporation then, dried residue is weighed.
-melt temperature, melting enthalpy and Tc: use the temperature variation of 20 ℃ of per minutes to measure by DSC.
-ethylene content: pass through infrared measurement.
-toughness/brittle transition temperature: measure according to Basell internalist methodology MTM 17324 (can ask for).
-modulus in flexure: measure according to ISO method 178.
-surrender and rupture stress: measure according to ISO method 527.
-surrender and elongation at break: measure according to ASTM method D-882.
-izod impact strength: measure according to ISO method 180.
-film mist degree: measure according to ASTM method D1003/61.
-energy-to-break under-20 ℃: measure according to Basell internalist methodology MTM 17324 (can ask for).
-film glossiness: measure according to ASTM method 523/89.
Embodiment 1-3
In the following embodiments, by under the condition of continuity, comprising that polypropylene and ethene prepare precursor composition in the manufactory of gas phase polymerization apparatus, the composition degraded that will obtain so then is to produce final composition of the present invention.
The catalyzer that uses comprises the catalyst component for preparing according to the embodiment 5 similar methods with EP-A-728769, but is to use microspheric MgCl
21.7C
2H
5OH replaces MgCl
22.1C
2H
5OH.This class catalyst component is with using as the dicyclopentyl dimethoxyl silane of external donor with triethyl aluminum (TEAl).The weight ratio of TEAl/ catalyst component is 5.The weight ratio of TEAl/ external donor is 4.
At first, in gas phase polymerization apparatus, in the presence of described catalyzer, produce multipolymer (A).This device comprises the barrel type reactor (lifter and downtake) of two interconnection.In lifter, set up the fast fluidization condition by means of recycle gas from gas-solid separator.
The multipolymer of producing like this (A) is sent into conventional fluidized-bed reactor continuously, wherein in the Gas-phase reactor in downstream, produce multipolymer (B).
The polymer beads that comes out from second reactor stands steam treatment, to remove reactive monomeric and volatile matter, carries out drying then.
In following table, provided the characteristic of the polymkeric substance of other operational conditions and generation.
With the polymer beads that obtains like this, it has constituted precursor composition, with 2, and 5-dimethyl-2,5-two (t-butyl peroxy) hexane mixes, and the latter is in subsequently the action of evocating that plays free radical in the processing of extruding.
The polymeric blends that has prepared the component that comprises following amount (weight part):
1) 99.72 parts polymer composition;
2) 0.03 part 2, two (t-butyl peroxy)-2 of 5-, 5-dimethylhexane; With
3) 0.05 part calcium stearate;
4) 0.05 part oil; With
5) 0.15 part additive stablizer.
Then, polymeric blends is placed twin screw extruder Berstorff (L/D=33) and under following operational condition, extruding:
The temperature of-feeding part: 190-210 ℃;
-melt temperature: 240 ℃;
The temperature of-die head part: 230 ℃;
-flow velocity: 12.6kg/h;
The rotating speed of-screw rod: 250rpm.
The composition of sample and salient features and main operational condition are reported in the table 1.
Table 1
| Embodiment | 1 | 2 | 3 |
| Polymerizing condition and poly-(propylene-be total to-ethene) analysis (A) that in gas phase polymerization apparatus, prepares | |||
| Temperature (℃) | 70 | 70 | 70 |
| C 2 -/(C 2 -+C 3 -) (gas ratio) (mol/mol) | 0.04 | 0.04 | 0.04 |
| Ethylene content (wt%) | 3.8 | 4 | 4 |
| MFR(g/10min) | 4.3 | 4 | 1.4 |
| Xylene soluble degree (wt%) | 7.3 | 8.5 | 7.9 |
| Polymerizing condition and poly-(propylene-be total to-ethene) analysis (B) that in second reactor, prepares | |||
| Temperature (℃) | 85 | 85 | 85 |
| C 2 -/(C 2 -+C 3 -) (gas ratio) (mol/mol) | 0.12 | 0.15 | 0.15 |
| Ethylene content (wt%) | 24 | 26 | 26 |
| The polymkeric substance compositional analysis | |||
| Multipolymer (B) content (wt%) | 20 | 19 | 24 |
| Ethylene content (wt%) | 8 | 8.2 | 9.3 |
| Ethylene content (wt%) in dissolving in the dimethylbenzene part | 22.5 | 22.2 | 23.5 |
| Ethylene content (wt%) in being insoluble to the dimethylbenzene part | 4 | 3.7 | 4.5 |
| The performance of precursor polymeric compositions | |||
| MFR(g/10min) | 2.8 | 2.3 | 0.97 |
| The limiting viscosity (dl/g) of solvable dimethylbenzene part | 2.54 | 2.47 | 2.45 |
| Modulus in flexure (MPa) | 560 | 490 | - |
| The performance of viscosity breaking polymer composition | |||
| MFR(g/10min) | 7.5 | 7.3 | 6.9 |
| Xylene soluble degree (wt%) | 24.1 | 23.5 | 28.8 |
| Dimethylbenzene nonsoluble (wt%) | 75.9 | 76.5 | 71.2 |
| Dissolve in the limiting viscosity (dl/g) of dimethylbenzene part | 1.69 | - | 1.58 |
| Be insoluble to the limiting viscosity (dl/g) of dimethylbenzene part | 1.49 | - | 1.57 |
| (100 μ m) hexane can extract part (wt%) on film | 3.6 | 3.8 | 3.8 |
| (100 μ m) hexane can extract part (wt%) on plaque | 5.5 | - | 7.4 |
| Melt temperature (℃) | 146.8 | 144.9 | 147.5 |
| Melting enthalpy (J/g) | 67.2 | 60.8 | 59.3 |
| Tc (℃) | 100.2 | 100.4 | 101.5 |
| Toughness/brittle transition temperature (℃) | -25 | -32 | -40 |
| Modulus in flexure (MPa) | 490 | 470 | 370 |
| Yielding stress (MPa) | 17 | 17 | 14 |
| Elongation at yield rate (%) | 16 | 16.4 | 19.8 |
| Rupture stress (MPa) | 24 | 16 | 17 |
| Elongation at break (%) | 422 | 420 | 424 |
| 23 ℃ of izod impact strength (kJ/m 2) | 15.8 | 14.1 | - |
| -20 ℃ of izod impact strength (kJ/m 2) | 2.6 | 2 | 3.6 |
| Energy-to-break under-20 ℃ (J) | 12.6 | 12.6 | 12.3 |
| Film (50 μ m) mist degree (%) | 12.9 | 17.7 | 11 |
| Film (50 μ m) glossiness (%) | 51 | 43 | 56.1 |
Illustrational composition has the hexane extractable matter level (HE) that is lower than 4wt%.The level of HE is measured the cast film according to 100 μ m thickness of FDA rules preparations.Measured value is significantly less than FDA limit (5.5wt%).
Modulus in flexure value that illustrational composition exhibiting is low (the modulus in flexure value is lower than 500MPa) and good low temperature impact properties (is about 12J-20 ℃ of following energy-to-break).
Use the cast film of 50 μ m thickness of illustrational composition production of the present invention also to show low modulus in tension value and tensile stress at yield value, and good optical property.
Table 1 has reported that in embodiment 1 and 2 composition described is before degraded and characteristic afterwards.With respect to the polymeric composition itself, the composition of chemical degradation has higher flowability, identical xylene soluble part content and lower a little modulus in flexure value.
Comparative example 1c-5c
The composition of embodiment 1c-5c carries out polymerization by the polymerization of order with propylene and ethene and prepares.
In first gas-phase polymerization reactor, by in gas phase, producing multipolymer (A) (propylene/ethylene copolymer) with continuous and constant flow charging pre-polymerized catalyst system, hydrogen (being used for the molecular weight regulation and control) and propylene and ethene.
The multipolymer of producing in first reactor is with the successive volume exhaust, and flows with successive after unreacted monomer is removed and introduce second Gas-phase reactor with gaseous hydrogen, propylene and the ethene of quantitative constant rate.
The polymer beads that comes out from second reactor stands steam treatment, to remove reactive monomeric and volatile matter, carries out drying then.
The catalyzer that uses be used for the identical of embodiment 1-3.
Polymer beads is without undergoing the chemical degradation of the MFRL value that is intended to obtain need, because the MFRL value of needs directly reaches in polymerization.
Table 2 has been reported the composition of polymerizing condition and such multipolymer that obtains.
Table 2
| The comparative example | 1c | 2c | 3c | 4c | 5c |
| Polymerizing condition and poly-(propylene-be total to-ethene) analysis (A) that in first reactor, prepares | |||||
| Temperature (℃) | 80 | 80 | 80 | 80 | 80 |
| Ethylene content (wt%) | 4.3 | 3.7 | 4.2 | 3.5 | 3.3 |
| MFR(g/10min) | 10.5 | 13.2 | 8.8 | 11.4 | 11.3 |
| Xylene soluble degree (wt%) | 8.0 | 6.8 | 7.9 | 6.5 | 6 |
| Polymerizing condition and poly-(propylene-be total to-ethene) analysis (calculating) (B) that in second reactor, prepares | |||||
| Temperature (℃) | 65 | 65 | 65 | 65 | 65 |
| C 2 -/(C 2 -+C 3 -) (gas ratio) (mol/mol) | 0.2 | 0.17 | 0.2 | 0.2 | 0.2 |
| Ethylene content (wt%) | 28 | 26 | 28 | 28 | 28 |
| Xylene soluble degree (wt%) | 94 | 94 | 94 | 94 | 94 |
| Polymer composition is analyzed and performance | |||||
| Multipolymer (B) content (wt%) | 16 | 33 | 21 | 15 | 18 |
| Ethylene content (wt%) | 8.0 | 11.2 | 9.1 | 7.1 | 7.8 |
| MFR(g/10min) | 8.0 | 7.7 | 6.7 | 9.3 | 9.7 |
| Xylene soluble degree (wt%) | 21.8 | 35.4 | 26.1 | 20.5 | 22.8 |
| Dissolve in the limiting viscosity (dl/g) of dimethylbenzene part | 1.61 | 1.83 | 1.62 | 1.61 | 1.45 |
| Be insoluble to the limiting viscosity (dl/g) of dimethylbenzene part | 1.65 | 1.55 | 1.67 | 1.65 | 1.60 |
| (100 μ m) hexane can extract part (wt%) on plaque | 7.5 | 13.1 | 9.4 | 7.2 | 8.8 |
With respect to composition 1 and 3, Comparative composition 1c-5c shows the limiting viscosity and the ethylene content of similarly final MFR value, xylene soluble and insoluble part.The random matrix of composition also is similar.
The hexane extractable matter is to measuring by 100 μ m thickness plaques of compression moulding preparation.The value of the hexane extractable matter that 100 μ m thickness plaques are measured is greater than the value of the hexane extractable matter that 100 μ m thickness cast films are measured; Yet this method is used when the material of the low amount of needs usually.With respect to the composition of comparative example 1c-5c, composition 1 and 3 shows significantly lower hexane extractable matter and the ratio between the xylene-soluble fraction.
Claims (10)
1. prolylene polymer composition, it has 3 to 20g/10min melt flow rate value, and it comprises:
A) one or more propylene copolymers of 50 to 90 weight %, it has under the room temperature that is not less than 85 weight % insoluble part content in the dimethylbenzene, and described propylene copolymer is selected from (A1) and comprises the propylene of 1 to 7 weight % ethene structural unit and the random copolymers of ethene; (A2) comprise the C of 2-10 weight %
4-C
8The propylene of alpha-olefin structural unit and one or more C
4-C
8The multipolymer of alpha-olefin; (A3) comprise the ethene structural unit of 0.5-5 weight % and the C of 2-6 weight %
4-C
8The propylene of alpha-olefin structural unit and ethene and one or more C
4-C
8The multipolymer of alpha-olefin; With
B) the ethene structural unit that comprises 8 to 40 weight % of 10 to 50 weight % and the randomly C of 1-10 weight %
4-C
8The multipolymer of the propylene of alpha-olefin structural unit;
Wherein said melt flow rate value, be called MFR (2) at this, comprise identical multipolymer (A) and precursor composition (B) with aforementioned proportion and degrade and reach by making, but the melt flow rate value before degraded, be called MFR (1) at this, be 0.1 to 5g/10min, MFR (2) is 1.5 to 20 with the ratio of MFR (1).
2. the composition of claim 1, wherein multipolymer (A) is that 60 to 85% weight and multipolymer (B) are 15 to 40% weight.
3. the composition of claim 1, wherein multipolymer (B) comprises the ethene structural unit of 8 to 30% weight.
4. the composition of claim 1, wherein multipolymer (B) comprises the ethene structural unit of 10 to 28% weight.
5. each method for compositions among the preparation claim 1-4, it may further comprise the steps:
1) prepares precursor composition by polymerization single polymerization monomer in the step of at least two orders, wherein multipolymer (A) and (B) independently the order step in prepare, in each step, in the presence of polymkeric substance that forms and the catalyzer that uses in the step in front, operate and so that the MFR of precursor composition (1) value reaches the 0.1 amount adding molecular weight regulator that arrives 5g/10min; With
2) with 1) the middle precursor composition for preparing carries out degradation treatment, so that the MFR of final composition (2) value reaches 3 to 20g/10min, the degraded ratio of representing with the ratio of MFR (2) and MFR (1) is 1.5 to 20.
6. the method for claim 5, wherein multipolymer (A) is prepared by the gas phase polymerization process that carries out in the district of at least two interconnection.
7. individual layer cast film wherein comprises the composition of claim 1.
8. multilayer cast film, wherein at least one layer comprises the composition of claim 1.
9. sheet material wherein comprises the composition of claim 1.
10. use the injection-mold container of the preparation of compositions of the composition that comprises claim 1.
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| EP01128193.8 | 2001-11-27 | ||
| EP01128193 | 2001-11-27 |
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| EP (1) | EP1448622B1 (en) |
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- 2002-11-22 CN CNB028235967A patent/CN100349929C/en not_active Expired - Fee Related
- 2002-11-22 RU RU2004119431/04A patent/RU2296772C2/en not_active IP Right Cessation
- 2002-11-22 AU AU2002352104A patent/AU2002352104A1/en not_active Abandoned
- 2002-11-22 DE DE60211012T patent/DE60211012T2/en not_active Expired - Lifetime
- 2002-11-22 KR KR10-2004-7007962A patent/KR20040062650A/en not_active Application Discontinuation
- 2002-11-22 US US10/496,270 patent/US7381773B2/en not_active Expired - Lifetime
- 2002-11-22 EP EP02787778A patent/EP1448622B1/en not_active Expired - Lifetime
- 2002-11-22 AT AT02787778T patent/ATE324387T1/en not_active IP Right Cessation
- 2002-11-22 PL PL02368462A patent/PL368462A1/en not_active Application Discontinuation
- 2002-11-22 CA CA002467812A patent/CA2467812A1/en not_active Abandoned
- 2002-11-22 WO PCT/EP2002/013145 patent/WO2003046021A1/en active IP Right Grant
- 2002-11-22 BR BRPI0206560A patent/BRPI0206560B1/en not_active IP Right Cessation
- 2002-11-22 ES ES02787778T patent/ES2262874T3/en not_active Expired - Lifetime
- 2002-11-22 JP JP2003547469A patent/JP4233454B2/en not_active Expired - Fee Related
- 2002-11-27 AR ARP020104550A patent/AR037444A1/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20040062650A (en) | 2004-07-07 |
| DE60211012T2 (en) | 2007-05-03 |
| JP2005510589A (en) | 2005-04-21 |
| EP1448622A1 (en) | 2004-08-25 |
| US20040266952A1 (en) | 2004-12-30 |
| RU2004119431A (en) | 2006-02-27 |
| US7381773B2 (en) | 2008-06-03 |
| PL368462A1 (en) | 2005-03-21 |
| WO2003046021A1 (en) | 2003-06-05 |
| CN1596272A (en) | 2005-03-16 |
| ES2262874T3 (en) | 2006-12-01 |
| DE60211012D1 (en) | 2006-06-01 |
| BR0206560A (en) | 2004-06-22 |
| ATE324387T1 (en) | 2006-05-15 |
| RU2296772C2 (en) | 2007-04-10 |
| CA2467812A1 (en) | 2003-06-05 |
| JP4233454B2 (en) | 2009-03-04 |
| EP1448622B1 (en) | 2006-04-26 |
| AR037444A1 (en) | 2004-11-10 |
| AU2002352104A1 (en) | 2003-06-10 |
| BRPI0206560B1 (en) | 2016-02-10 |
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